Relationship of Indoor N02 Concentrations to Use of Unvented Gas Appliances

In preparation for a prospective study of the relationship of residential nitrogen dioxide exposure and respiratory infections in infants, we conducted a pilot study to assess NO₂ concentrations in a sample of homes in Albuquerque, New Mexico. The methods used to characterize concentrations are described. Three locations in 144 homes were monitored with passive diffusion samplers for two two-week cycles during November and December 1984. Two-week average NO₂ concentrations in the activity room ranged from 2.0 to 168.7 ppb. NO₂ concentrations in the activity room and the infant’s bedroom were fivefold higher in homes with gas stoves than in homes with electric stoves. Sixty-four percent of homes with gas stoves had activity room concentrations that exceeded the highest outdoor concentration. Multiple regression models Indicated that the outdoor concentration, use of a gas stove, particularly one with pilot lights, presence of a gas dryer in the living area, and use of a floor or wall furnace contributed to NO₂ concentrations. Use of a toaster or microwave oven in a house with a gas stove reduced NO₂ concentrations. The results of this study demonstrate a broad range of NO₂ concentrations in Albuquerque. We conclude with suggestions for an exposure assessment strategy that would be valid and feasible in the context of a large epidemiologic study of the health effects of NO₂.     

Modeling the intra-urban variability of outdoor traffic pollution in Oslo,Norway—A GA2LEN project

Traffic is a major source of air pollutants in urban environments, and exposure to these pollutants may be associated with adverse health effects. However, inconsistencies in observational epidemiological studies may be caused by differential measurement errors in various approaches in assessing exposure.We aimed to evaluate a simple method for assessing outdoor air pollutant concentrations in Oslo, Norway, through a land-use regression method.Samples of nitrogen oxides (NO_x) were collected in two different weeks using Ogawa passive diffusion samplers simultaneously at 80 locations across Oslo. Independent variables used in subsequent regression models as predictors of the pollutants were derived using the Arc 9 geographic information system (GIS) software. Indicators of land use, traffic, population density, and physical geography were tested.The final regression model yielded an adjusted coefficient of determination (R²) of 0.77 for nitrogen dioxide (NO₂), 0.66 for nitric oxide (NO), and 0.73 for NO_x.The results suggest that a good predictive exposure model can be derived from this approach, which can be used to estimate long-term small-area variation in concentrations for individual exposure assessment in epidemiological studies in a highly cost-effective way. These small-area variations in traffic pollution are important since they may have associations with health effects.     

Potential interferences in photolytic nitrogen dioxide converters for ambient air monitoring: Evaluation of a prototype

ABSTRACT

Mixing ratios of the criteria air contaminant nitrogen dioxide (NO₂) are commonly quantified by reduction to nitric oxide (NO) using a photolytic converter followed by NO-O₃ chemiluminescence (CL). In this work, the performance of a photolytic NO₂ converter prototype originally designed for continuous emission monitoring and emitting light at 395 nm was evaluated. Mixing ratios of NO₂ and NO_x (= NO + NO₂) entering and exiting the converter were monitored by blue diode laser cavity ring-down spectroscopy (CRDS). The NO₂ photolysis frequency was determined by measuring the rate of conversion to NO as a function of converter residence time and found to be 4.2 s^?1. A maximum 96% conversion of NO₂ to NO over a large dynamic range was achieved at a residence time of (1.5 ± 0.3) s, independent of relative humidity. Interferences from odd nitrogen (NO_y) species such as peroxyacyl nitrates (PAN; RC(O)O₂NO₂), alkyl nitrates (AN; RONO₂), nitrous acid (HONO), and nitric acid (HNO₃) were evaluated by operating the prototype converter outside its optimum operating range (i.e., at higher pressure and longer residence time) for easier quantification of interferences. Four mechanisms that generate artifacts and interferences were identified as follows: direct photolysis, foremost of HONO at a rate constant of 6% that of NO₂; thermal decomposition, primarily of PAN; surface promoted photochemistry; and secondary chemistry in the connecting tubing. These interferences are likely present to a certain degree in all photolytic converters currently in use but are rarely evaluated or reported. Recommendations for improved performance of photolytic converters include operating at lower cell pressure and higher flow rates, thermal management that ideally results in a match of photolysis cell temperature with ambient conditions, and minimization of connecting tubing length. When properly implemented, these interferences can be made negligibly small when measuring NO₂ in ambient air.

Implications: A new near-UV photolytic converter for measurement of the criteria pollutant nitrogen dioxide (NO₂) in ambient air by CL was characterized. Four mechanisms that generate interferences were identified and investigated experimentally: direct photolysis of HONO which occurred at a rate constant 6% that of NO₂, thermal decomposition of PAN and N₂O₅, surface promoted chemistry involving HNO₃, and secondary chemistry involving NO in the tubing connecting the converter and CL analyzer. These interferences are predicted to occur in all NO₂ P-CL systems but can be avoided by appropriate thermal management and operating at high flow rates.     

Indoor Nitrogen Dioxide Exposure and Children’s Pulmonary Function

Elevated concentrations of nitrogen dioxide (NO₂) are produced in the home by the use of unvented gas appliances. In studies on potential health effects of Indoor exposure to NO₂, exposure has mostly been estimated from the presence or absence of sources like gas cookers in the home. This leads to misclassification of exposure, as NO₂ concentrations in the home depend also on source use, ventilation habits, time budgets, etc. The availability of cheap, passive monitoring devices has made it possible to measure Indoor concentrations of NO₂ directly in health effects studies, albeit with averaging times of one to several days. So far, it has not been evaluated whether this increases the sensitivity of a study to detect health effects of NO₂. In this paper, a comparison is made between NO₂ sources and weekly average indoor NO₂ measurements, as predictors of pulmonary function in a study among children aged 6–12 years.

The relationship between exposure and lung functions was found to be generally non-significant in this study. The results further suggested that in this study, measuring Indoor NO₂ concentrations with passive monitors offered no advantage over the simple use of source presence as exposure variable.     

Back-extrapolation of estimates of exposure from current land-use regression models

Land use regression has been used in epidemiologic studies to estimate long-term exposure to air pollution within cities. The models are often developed toward the end of the study using recent air pollution data. Given that there may be spatially-dependent temporal trends in urban air pollution and that there is interest for epidemiologists in assessing period-specific exposures, especially early-life exposure, methods are required to extrapolate these models back in time. We present herein three new methods to back-extrapolate land use regression models. During three two-week periods in 2005–2006, we monitored nitrogen dioxide (NO₂) at about 130 locations in Montreal, Quebec, and then developed a land-use regression (LUR) model. Our three extrapolation methods entailed multiplying the predicted concentrations of NO₂ by the ratio of past estimates of concentrations from fixed-site monitors, such that they reflected the change in the spatial structure of NO₂ from measurements at fixed-site monitors. The specific methods depended on the availability of land use and traffic-related data, and we back-extrapolated the LUR model to 10 and 20 years into the past. We then applied these estimates to residential information from subjects enrolled in a case–control study of postmenopausal breast cancer that was conducted in 1996.Observed and predicted concentrations of NO₂ in Montreal decreased and were correlated in time. The estimated concentrations using the three extrapolation methods had similar distributions, except that one method yielded slightly lower values. The spatial distributions varied slightly between methods. In the analysis of the breast cancer study, the odds ratios were insensitive to the method but varied with time: for a 5 ppb increase in NO₂ using the 2006 LUR the odds ratio (OR) was about 1.4 and the ORs in predicted past concentrations of NO₂ varied (OR～1.2 for 1985 and OR～1.3–1.5 for 1996). Thus, the ORs per unit exposure increased with time as the range and variance of the spatial distributions decreased, and this is due partly to the regression coefficient being approximately inversely proportional to the variance of exposure. Changing spatial variability complicates interpretation and this may have important implications for the management of risk. Further studies are needed to estimate the accuracy of the different methods.     

The use of wind fields in a land use regression model to predict air pollution concentrations for health exposure studies

A methodology is developed to include wind flow effects in land use regression (LUR) models for predicting nitrogen dioxide (NO₂) concentrations for health exposure studies. NO₂ is widely used in health studies as an indicator of traffic-generated air pollution in urban areas. Incorporation of high-resolution interpolated observed wind direction from a network of 38 weather stations in a LUR model improved NO₂ concentration estimates in densely populated, high traffic and industrial/business areas in Toronto-Hamilton urban airshed (THUA) of Ontario, Canada. These small-area variations in air pollution concentrations that are probably more important for health exposure studies may not be detected by sparse continuous air pollution monitoring network or conventional interpolation methods. Observed wind fields were also compared with wind fields generated by Global Environmental Multiscale-High resolution Model Application Project (GEM-HiMAP) to explore the feasibility of using regional weather forecasting model simulated wind fields in LUR models when observed data are either sparse or not available. While GEM-HiMAP predicted wind fields well at large scales, it was unable to resolve wind flow patterns at smaller scales. These results suggest caution and careful evaluation of regional weather forecasting model simulated wind fields before incorporating into human exposure models for health studies. This study has demonstrated that wind fields may be integrated into the land use regression framework. Such integration has a discernable influence on both the overall model prediction and perhaps more importantly for health effects assessment on the relative spatial distribution of traffic pollution throughout the THUA. Methodology developed in this study may be applied in other large urban areas across the world.     

The Plume Volume Molar Ratio Method for Determining NO2/NOx Ratios in Modeling—Part I: Methodology

ABSTRACT

During New Source Review modeling of proposed major sources of oxides of nitrogen (NO_x), maximum impacts are often predicted to occur very close to the source. At the same time, current modeling guidance recommends techniques that may be overly conservative in estimating the fraction of nitrogen dioxide (NO₂) in these plumes. A new technique called the Plume Volume Molar Ratio Method (PVMRM) is being proposed that simulates both chemistry and dispersion to better estimate the fraction of NO₂. This paper documents the methodology behind the technique. A follow-up pa-per¹ will evaluate its performance against a number of databases. This method is designed to realistically predict NO₂ fraction at close-in receptors yet still provide conservative estimates so that the air quality standards can be protected.     

Nitrogen dioxide inhalation induces genotoxicity in rats

Nitrogen dioxide (NO₂) is a ubiquitous reactive free-radical gas, which has been associated with momentary and chronic health effects. In the present study, comet, micronucleus (MN) and DNA–protein crosslinks (DPC) assays were used to investigate the genotoxicity following in vivo inhalation exposure of rats to NO₂. The results show that inhalation exposure of rats to NO₂ induced DNA strand breakage and the formation of DPC in the cells from various internal organs (brain, lung, liver, spleen, kidney and heart), as well as resulted in obvious increase of MN frequency in the bone marrow cells of rats. Furthermore, above genotoxic responses showed significant linear dose-dependent manners. These results implicate that NO₂ is a genotoxic agent and these observations are informative for understanding the mechanisms of adverse effects of nitrogen dioxide.     

Simultaneous Sulfur Dioxide and Nitrogen Dioxide Removal by Calcium Hydroxide and Calcium Silicate Solids

ABSTRACT

At conditions typical of a bag filter exposed to a coal-fired flue gas that has been adiabatically cooled with water, calcium hydroxide and calcium silicate solids were exposed to a dilute, humidified gas stream of nitrogen dioxide (NO₂) and sulfur dioxide (SO₂) in a packed-bed reactor. A prior study found that NO₂ reacted readily with surface water of alkaline and non-alkaline solids to produce nitrate, nitrite, and nitric oxide (NO). With SO₂ present in the gas stream, NO₂ also reacted with S(IV), a product of SO₂ removal, on the exterior of an alkaline solid. The oxidation of S(IV) to S(VI) by oxygen reduced the availability of S(IV) and lowered removal of NO₂. Subsequent acidification of the sorbent by the removal of NO₂ and SO₂ facilitated the production of NO. However, the conversion of nitrous acid to sulfur-nitrogen compounds reduced NO production and enhanced SO₂ removal. A reactor model based on empirical and semi-empirical rate expressions predicted rates of SO₂ removal, NO₂ removal, and NO production by calcium silicate solids. Rate expressions from the reactor model were inserted into a second program, which predicted the removal of SO₂ and NO_x by a continuous process, such as the collection of alkaline solids in a baghouse. The continuous process model, depending upon inlet conditions, predicted 30-40% removal for NO and 50-90% removal for SO₂. These x 2 results are relevant to dry scrubbing technology for combined SO₂ and NO_x removal that first oxidizes NO to NO₂ by the addition of methanol into the flue duct.     

Estimated long-term outdoor air pollution concentrations in a cohort study

Several recent studies associated long-term exposure to air pollution with increased mortality. An ongoing cohort study, the Netherlands Cohort Study on Diet and Cancer (NLCS), was used to study the association between long-term exposure to traffic-related air pollution and mortality. Following on a previous exposure assessment study in the NLCS, we improved the exposure assessment methods.Long-term exposure to nitrogen dioxide (NO₂), nitrogen oxide (NO), black smoke (BS), and sulphur dioxide (SO₂) was estimated. Exposure at each home address (N=21 868) was considered as a function of a regional, an urban and a local component. The regional component was estimated using inverse distance weighed interpolation of measurement data from regional background sites in a national monitoring network. Regression models with urban concentrations as dependent variables, and number of inhabitants in different buffers and land use variables, derived with a Geographic Information System (GIS), as predictor variables were used to estimate the urban component. The local component was assessed using a GIS and a digital road network with linked traffic intensities. Traffic intensity on the nearest road and on the nearest major road, and the sum of traffic intensity in a buffer of 100 m around each home address were assessed. Further, a quantitative estimate of the local component was estimated.The regression models to estimate the urban component explained 67%, 46%, 49% and 35% of the variances of NO₂, NO, BS, and SO₂ concentrations, respectively. Overall regression models which incorporated the regional, urban and local component explained 84%, 44%, 59% and 56% of the variability in concentrations for NO₂, NO, BS and SO₂, respectively.We were able to develop an exposure assessment model using GIS methods and traffic intensities that explained a large part of the variations in outdoor air pollution concentrations.     

A Short-Term Diffusive Sampler for Nitrogen Dioxide Monitoring in Epidemiology

An automated timed exposure diffusive sampler (TEDS) for sampling nitrogen dioxide (NO₂) was developed for use in epidemiological studies. The TEDS sequentially exposes four passive sampling devices (PSD) by microprocessor controlled valves while a pump and air flow guide prevent sampler "starvation." Two TEDS units and two portable, real-time NO₂ monitors were tested for accuracy, precision, sensitivity, and linearity of response. The accuracy of the TEDS was within 10 percent of the calibrated NO₂ values, and precision was within 10 percent of the means of the measured values. The TEDS sensitivity was 20 to 30 ppb-hour for NO₂. Co-location of the TEDS with a chemiluminescent NOX monitor (EPA reference method) showed similar responses to ambient NO₂ (R2 = 0.9991). TEDS allows better time resolution than traditional diffusive samplers (i.e., Palmes tube) while sharing their ability to sample a variety of gases.     

The Chattanooga School Children Study: Effects of Community Exposure to Nitrogen Dioxide

Elementary schools in four areas of Greater Chattanooga were selected for a study of the effects of community exposure to nitrogen dioxide. One area, in close proximity to a large TNT plant, had high NO₂ exposure, another had relatively high suspended particulate exposure, and two areas served as “clean” controls. The similarity of the economic levels of the High-NO₂ and Control areas and the moderately lower economic level of the High-Particulate area were documented. Pollutant concentrations for NO₂ gas, suspended nitrates and sulfates, total suspended particulates, and soiling index were measured at stations located within the study areas. Ventilatory performance of second-grade school children in the High-NO₂ exposure area was significantly lower than the performance of children in the Control areas. The data suggested that ventilatory performance was adversely affected only when an NO₂ threshold was exceeded but that above this threshold no further impairment of performance could be detected.     

Probabilistic assessment of the potential indoor air impacts of vent-free gas heating appliances in energy-efficient homes in the United States

Use of vent-free gas heating appliances for supplemental heating in U.S. homes is increasing. However, there is currently a lack of information on the potential impact of these appliances on indoor air quality for homes constructed according to energy-efficient and green building standards. A probabilistic analysis was conducted to estimate the impact of vent-free gas heating appliances on indoor air concentrations of carbon monoxide (CO), nitrogen dioxide (NO₂), carbon dioxide (CO₂), water vapor, and oxygen in “tight” energy-efficient homes in the United States. A total of 20,000 simulations were conducted for each Department of Energy (DOE) heating region to capture a wide range of home sizes, appliance features, and conditions, by varying a number of parameters, e.g., room volume, house volume, outdoor humidity, air exchange rates, appliance input rates (Btu/hr), and house heat loss factors. Predicted airborne levels of CO were below the U.S. Environmental Protection Agency (EPA) standard of 9 ppm for all modeled cases. The airborne concentrations of NO₂ were below the U.S. Consumer Product Safety Commission (CPSC) guideline of 0.3 ppm and the Health Canada benchmark of 0.25 ppm in all cases and were below the World Health Organization (WHO) standard of 0.11 ppm in 99–100% of all cases. Predicted levels of CO₂ were below the Health Canada standard of 3500 ppm for all simulated cases. Oxygen levels in the room of vent-free heating appliance use were not significantly reduced. The great majority of cases in all DOE regions were associated with relative humidity (RH) levels from all indoor water vapor sources that were less than the EPA-recommended 70% RH maximum to avoid active mold and mildew growth. The conclusion of this investigation is that when installed in accordance with the manufacturer’s instructions, vent-free gas heating appliances maintain acceptable indoor air quality in tight energy-efficient homes, as defined by the standards referenced in this report.

Implications: Probabilistic modeling of indoor air concentrations of carbon monoxide (CO), nitrogen dioxide (NO₂), carbon dioxide (CO₂), water vapor, and oxygen associated with use of vent-free gas heating appliances provides new data indicating that uses of these devices are consistent with acceptable indoor air quality in “tight” energy-efficient homes in the United States. This study will provide authoritative bodies such as the International Code Council with definitive information that will assist in the development of future versions of national building codes, and will provide evaluation of the performance of unvented gas heating products in energy conservation homes.     

Personal exposures to NO2 in the EXPOLIS-study: relation to residential indoor,outdoor and workplace concentrations in Basel,Helsinki and Prague

Personal exposures, residential indoor, outdoor and workplace levels of nitrogen dioxide (NO₂) were measured for 262 urban adult (25–55 years) participants in three EXPOLIS centres (Basel; Switzerland, Helsinki; Finland, and Prague; Czech Republic) using passive samplers for 48-h sampling periods during 1996–1997. The average residential outdoor and indoor NO₂ levels were lowest in Helsinki (24±12 and 18±11 μg m⁻³, respectively), highest in Prague (61±20 and 43±23 μg m⁻³), with Basel in between (36±13 and 27±13 μg m⁻³). Average workplace NO₂ levels, however, were highest in Basel (36±24 μg m⁻³), lowest in Helsinki (27±15 μg m⁻³), with Prague in between (30±18 μg m⁻³). A time-weighted microenvironmental exposure model explained 74% of the personal NO₂ exposure variation in all centres and in average 88% of the exposures. Log-linear regression models, using residential outdoor measurements (fixed site monitoring) combined with residential and work characteristics (i.e. work location, using gas appliances and keeping windows open), explained 48% (37%) of the personal NO₂ exposure variation. Regression models based on ambient fixed site concentrations alone explained only 11–19% of personal NO₂ exposure variation. Thus, ambient fixed site monitoring alone was a poor predictor for personal NO₂ exposure variation, but adding personal questionnaire information can significantly improve the predicting power.     

Evaluation of nitrogen dioxide photolysis rates in an urban area using data from the 1997 Southern California Ozone Study

The photolysis of nitrogen dioxide and formaldehyde are two of the most influential reactions in the formation of photochemical air pollution, and their rates are computed using actinic flux determined from a radiative transfer model. In this study, we compare predicted and measured nitrogen dioxide photolysis rate coefficients (j_NO2). We used the Tropospheric Ultraviolet-Visible (TUV) radiation transfer model to predict j_NO2 values corresponding to measurements performed in Riverside, California as part of the 1997 Southern California Ozone Study (SCOS’97). Spectrally resolved irradiance measured at the same site allowed us to determine atmospheric optical properties, such as aerosol optical depth and total ozone column, that are needed as inputs for the radiative transfer model. Matching measurements of aerosol optical depth, ozone column, and j_NO2 were obtained for 14 days during SCOS’97. By using collocated measurements of the light extinction caused by aerosols and ozone over the full height of the atmosphere as model input, it was possible to predict sudden changes in j_NO2 resulting from atmospheric variability. While the diurnal profile of the rate coefficient was readily reproduced, j_NO2 model predicted values were found to be consistently higher than measured values. The bias between measured and predicted values was 17–36%, depending on the assumed single scattering albedo. By statistical analysis, we restricted the most likely values of the single scattering albedo to a range that produced bias on the order of 20–25%. It is likely that measurement error is responsible for a significant part of the bias. The aerosol single scattering albedo was found to be a major source of uncertainty in radiative transfer model predictions. Our best estimate indicates its average value at UV-wavelengths for the period of interest is between 0.77 and 0.85.     

The Plume Volume Molar Ratio Method for Determining NO2/NOx Ratios in Modeling—Part II: Evaluation Studies

ABSTRACT

A previous paper¹ discusses the methodology for a new method for deriving the nitrogen dioxide/nitrogen oxide (NO₂/NO_x) ratio in plumes that originally are composed mainly of (NO_x). It is called the Plume Volume Molar Ratio Method (PVMRM). This paper documents its performance against six different data sets. These performance evaluations show that the PVMRM can realistically predict the NO₂ fraction at close-in receptors yet still provide conservative estimates so that the air quality standards can be protected.     

Solar driven nitrous acid formation on building material surfaces containing titanium dioxide: A concern for air quality in urban areas?

The photoenhanced uptake of nitrogen dioxide (NO₂) to the surface of commercially available self-cleaning window glass has been studied under controlled laboratory conditions. This material is one of an array of modern building products which incorporate titanium dioxide (TiO₂) nanoparticles and are finding increasing use in populated urban areas. Amongst the principal drivers for the use of these materials is that they are thought to facilitate the irreversible removal of pollutants such as NO₂ and organic molecules from the atmosphere and thus act to remediate air quality. While it appears that TiO₂ materials do indeed remove organic molecules from built environments, in this study we show that the photoenhanced uptake of NO₂ to one example material, self-cleaning window glass, is in fact accompanied by the substantial formation (50–70%) of gaseous nitrous acid (HONO). This finding has direct and serious implications for the use of these materials in urban areas. Not only is HONO a harmful respiratory irritant, it is also readily photolysed by solar radiation leading to the formation of hydroxyl radicals (OH) together with the re-release of NO_x as NO. The net effect of subsequent OH initiated chemistry can then be the further degradation of air quality through the formation of secondary pollutants such as ozone and VOC oxidation products. In summary, we suggest that a scientifically conceived technical strategy for air quality remediation based on this technology, while widely perceived as universally beneficial, could in fact have effects precisely opposite to those intended.     

Street-level concentrations of nitrogen dioxide and suspended particulate matter in Hong Kong

The concentrations of respirable suspended particulates (PM₁₀), fine suspended particulates (PM_2.5) and nitrogen dioxide (NO₂) were measured in various locations over the territory of Hong Kong. In order to study the contributions of these pollutants from motor vehicles and their characteristics, the attention was focused on the roadside, street-level concentrations. A statistical analysis of the sampling results was conducted to obtain general characteristics of the roadside particulate and nitrogen dioxide pollution and to investigate the effects of traffic volume and meteorological factors on the pollution levels. High correlation coefficients are found between PM₁₀, PM_2.5 and NO₂ concentration.     

Analysis of air quality within a street canyon using statistical and dispersion modelling techniques

The dispersion model, ADMS-Urban, alongside the statistical modelling technique, generalized additive modelling, have been used to predict hourly NO_x and nitrogen dioxide (NO₂) concentrations at a busy street canyon location and the results compared with measurements. Generalized additive models (GAMs) were constructed for NO₂ and NO_x concentrations using input data required to run ADMS-Urban. Bivariate polar plots have been produced from the wind flow (speed and direction) and pollution data (measured and predicted concentrations) to provide further information regarding the complex wind-pollutant interactions in an urban street canyon. The predictions made with the GAMs show excellent agreement with measured concentrations at this location, reproducing both the magnitude of NO_x and NO₂ concentrations and also the wind speed-wind direction dependence of pollutant sources within the canyon. However, the predictions made with ADMS-Urban under-estimated the measured NO_x by 11% and NO₂ by 21% and there are clear differences in the bivariate polar plots. Several sensitivity tests were carried out with ADMS-Urban in an attempt to produce predictions in closer agreement to those measured at Gillygate. Increasing the primary NO₂ fraction in ADMS-Urban (from 10% to 20%) had a considerable effect on the predictions made with this model, increasing NO₂ predictions by ∼20%. However, the bivariate plots still showed major differences to those of the measurements. This work illustrates that generalized additive modelling is a useful tool for investigating complex wind-pollutant interactions within a street canyon.     

Influence of photolysis on multispectral photoacoustic measurement of nitrogen dioxide concentration

Multispectral photoacoustic instruments are commonly used to measure aerosol and nitrogen dioxide (NO₂) light absorption coefficients to determine the radiation budget of the atmosphere. Here a new photoacoustic system is developed to explore the effect of photolysis on the measured signal in a multispectral photoacoustic spectrometer. In this system, a 405-nm laser is used primarily as light source for photolysis. Additionally, a well-overlapped 532-nm laser, modulated at the resonant frequency of the photoacoustic instrument, is used to probe the NO₂ concentration. As a result, the photolysis effect at 405 nm can be observed by the photoacoustic instrument through the 532-nm laser. This work determines an 11% reduction of the photoacoustic signal caused by the photolysis effect for typical conditions, which needs to be taken into account when calibrating multispectral photoacoustic spectrometers with NO₂.

Implications: Multispectral photoacoustic instruments are commonly used to measure aerosol and nitrogen dioxide (NO₂) light absorption coefficients to determine the radiation budget of the atmosphere. A 405-nm laser is often used in these multispectral photoacoustic instruments. Although NO₂ absorbs strongly at 405 nm, it also has a strong photolysis pathway that is accessible by light of the same wavelength. Photolysis reduces the photoacoustic signal, necessitating special care when interpreting photoacoustic measurements. This paper offers a method for the multispectral photoacoustic instrument user to quantify the influence of the 405-nm NO₂ photolysis effect on the photoacoustic signal.